Preparation of polycyclic ketones

ABSTRACT

This specification discloses a method for the preparation of a polycyclic ketone. The polycyclic ketone has at least two rings. At least one of these rings is an aromatic ring and another of these rings contains, as part of its ring structure, the carbon atom of a keto group. These latter two rings share two carbon atoms as part of their ring structures. In the method, an olefin or an acetylene is reacted with an aromatic ketone. This aromatic ketone has at least one aromatic ring and the aromatic ring has a side chain containing a keto group. The carbon atom on one side of the keto group has at least one hydrogen atom connected thereto and the carbon atom on the other side of the keto group is part of the aromatic ring. The reaction of the olefin or acetylene with the aromatic ketone is carried out in the presence of an ion of manganese, cerium, or vanadium in a higher valent form.

[ Jan. 14, 1975 PREPARATION OF POLYCYCLIC KETONES [75] Inventors: El Ahmadi I. Heiba, Princeton;

Ralph M. Dessau, Highland Park, both of NJ.

[73] Assignee: Mobil Oil Corporation, New York,

[22] Filed: Apr. 5, 1972 [21] Appl. No.: 241,380

Related US. Application Data [52] US. Cl... 260/332.3 P, 260/297 B, 260/326.16, 260/346.2 R, 260/448.2 B, 260/482 C, 260/488 CD, 260/581, 260/590, 260/621 H,

260/624 C [51] Int. Cl. C07c 45/00 [58] Field of Search 260/590, 297 B, 326.16,

[56] References Cited UNITED STATES PATENTS 3,006,976 10/1961 Shaw et al. 260/590 X 3,341,601 9/1967 Mertzweiller 260/590 X Primary Examiner-Leon Zitver Assistant Examiner-Norman P. Morgenstern Attorney, Agent, or Firm 'Vincent .I. Frilette:

Andrew L. Gaboriault [57] ABSTRACT This specification disclosesa method for the preparation of a polycyclic ketone. The polycyclic ketone has at least two rings. At least one of these rings is an aromatic ring and another of these rings contains, as part of its ringstructure, the carbon atom of a keto group. These latter two rings share two carbon atoms as part of their ring structures. In the method, an olefin or an acetylene is reacted with an aromatic ketone. This aromatic ketone has at least one aromatic ring and the aromatic ring has a side chain containing a kcto group. The carbon atom on one side of the keto group has at least one hydrogen atom connected thereto and the carbon atom on the other side of the keto group is part of the aromatic ring. The reaction of the olefin or acetylene with the aromatic ketone is carried out in the presence of an ion of manganese, cerium, or vanadium in a higher valent form.

12 Claims, No Drawings CROSS REFERENCE TO RELATED APPLICATIONS This application is a continuation-in-part of our pending application Ser. No. 828,342, filed May 27, 1969 and now abandoned. Application Ser. No. 828,342 is a continuation-in-part of our then copending application Ser. No. 714,447 filed March 20, 1968,

but now abandoned and is a continuation-in-part of our copending application Ser. No. 755,732, filed Aug. 27, 1968 and now abandoned. Application Ser. No. 755,732 is a continuation-in-part of application Ser. No. 714,447 filed March 20, 1968.

BACKGROUND OF THE INVENTION 1. Field of the Invention The field of the invention is a method for the preparation of a polycyclic ketone.

2. Description of the Prior Art ion of manganese, cerium, or vanadium in a higher valent form.

BRIEF SUMMARY OF THE INVENTION In accordance with the invention, there is provided a method for preparing a polycyclic ketone. The poly- 3O cyclic ketone has at least two rings. At least one of these rings is an aromatic ring and another of these V rings contains, as part of its ring structure, the carbon atom of a keto group. These latter two rings share two carbon atoms as part of their ring structures. In the method, an olefin or an acetylene is reacted with an aromatic ketone. This aromatic ketone has at least one aromatic ring and the aromatic ring has a side chain containing a keto group. The carbon atom on one side of the keto group has at least one hydrogen atom connected thereto and the carbon atom on the other side of the keto group is part of the aromatic ring. The reaction of the olefin or acetylene with the aromatic ketone is carried out in the presence of an ion of manganese, cerium, or vanadium in a higher valent form.

DESCRIPTION OF THE PREFERRED EMBODIMENTS At the outset, it may be of interest to note that polycyclic ketones in general are useful as intermediates for the production of commercial antioxidants, such as alpha-naphthols and alpha-naphtholamines, and metal deactivators. They are also useful as intermediates for the production of insecticides and chelating agents. Further and more detailed reference to the utility of the polycyclic ketones will be made hereinafter.

The reaction whereby the polycyclic ketones may be prepared can be described in equation form wherein, for purposes of illustration, ethylene will be the olefin, phenyl methyl ketone will be the aromatic ketone, and manganese will be the metal ion. The equations are as follows:

CH O CH O CIH (III C-CH Mn CII'I -C-C H CH /CH CH\ CH CH CH Mn' if 1 CH O (In this equation, CIH C C --CH is a free radical.)

ll CH /CH \CH CH O a cln c -c -C H +CH =CII CH\ CH CH /O cln c -c CH -cu qn CH /CH CH O (In Equatlon 2, CH ('2 C CH -CII -C H 1s a free radical.)

l C H CH Thus, the overall reaction is:

showing that one mole of aromatic ketone and one mole of olefin in the presence of two moles of manganic ion give one mole of polycyclic ketone, two moles of manganous ion, and two moles of hydrogen ion. As shown in Equation 1, the

free radical is produced when the manganic ion is reacted with the aromatic ketone. According to the reaction of Equation 2, the reactive species,

adds to the double bond of the olefin, forming the free radical According to the Equation 3, the ketone product of Equation 2 cyclizes.

In the reaction illustrated above, the aromatic ketone is phenyl methyl ketone. This aromatic ketone has at least one aromatic ring, i.e., the benzene ring, and has a side chain containing a keto group, i.e., the side chain being 2 -c CH3 and the keto group being of the product and the cyclohexene ring on the right side of the product. The two carbon atoms,

\ C II C are shared by each of the two rings. Further, the carbon atom of the keto group, the

0 ll C is part of the ring structure of the cyclohexene ring.

Still further, in the reaction illustrated above, the metal ion is manganese and manganese ion can have higher and lower valent formspln the reaction illustrated, the manganese ion has a valence of 3, i.e., the manganese ion is in a higher valent form. During the C reaction, the manganic ion is reduced to manganous ion wherein the manganese ion has a valence of 2, i.e., 5 the manganese ion is in a lower valent form. It will be noted that the manganic ion forms a free radical from the aromatic ketone. (e)

The explanation of the foregoing reaction mecha- I nism is intended only to be illustrative and not limiting. I o I The olefin employed in the method of the invention may be a monoolefin or may contain two or more dou- 0 ble bonds. Preferably, the olefin is a monoolefin containing not more than four carbon atoms. Specifically, I

ethylene, propylene, the n-butylenes, or isobutylene is preferred. Of these, ethylene is preferred. However, S

other olefins such as the pentenes, hexenes, heptenes,

and octenes may be employed. Olefin oligomers ar The dangling valences in the aromatic ketones above useful, such as propylene tetramer and isobutylene triy be y suitable radieal, such as y g or alkyl,

mer. Also suitable are open chain, conjugated or unalkenyl, or y groups The alkyl g p y for conjugated diolefins having 3 to 8 carbons and includample, methyl, ethyl, P PYL y 0f p y g p ing allene, butadiene, isoprene, pentadiene, hexadiene, The dangling Valahees Oh the aromatic ring y be heptadiene, and diisobutenyl. Also of use are open g p Such as R, an ha ogen Where R iS chain olefins having more than two double bonds, an alkyl group such as those j mehti0hedsometimes designated oligoolefins, such as hexatriene. The reaetieh 0f the Olefin 0r aeetylene with the The acetylene employed in the meth d f th i matic ketone is carried out, also as stated, in the prestion may be a monoacetyl ne or may t i two or ence of an ion of a metal. The metal is manganese, cemore triple bonds. Acetylenes whi h m b l d rium, or vanadium. Each of these metals forms reducinclude ethine, allyl ne, th b t m h ible metal ions having lower or higher valent forms and ynes, heptynes, and octynes. Hydrocarbons having is capable of existing in either of the two forms. The ion both double and triple bonds, i.e., compounds which is i higher valent form and, during the reaction, I are both olefins and acetylenes, ar of val h as duced to a lower valent form and forms a free radical butenyne, 1,6-heptadiene-3-yne d 1,7- from the aromatic ketone. In their higher valency Mixtures of olefins and/0r aceylenes may be employed, states, the ions of these metals have a relatively good The olefin may also contain a substituent which con- Oxidation Potential and, in their lower valency states, tains oxygen, a halide, or a metal. tend to be stable and reoxidizable to the higher valency The aromatic ketone employed in the method of the Stateinvention has, as stated, at least one aromatic ring, a h metal ion in h gh r valent f m m y be pr vi side chain on the aromatic ring containing a k t by any compound of the metal that will provide ions of group, the carbon atom on one side of the k to group the metal in the reaction mixture. Stated otherwise, it having at least one hydrogen atom connected thereto, iS m aterial what compound provides the metal ions and the carbon atom on the other side of the keto l g as the compound wi l, in h pr n f h group being part of the aromatic ring, The r i olefin, acetylene, or aromatic ketone reactants, or solring may be a benzene ring, a thiophene ring, a furan vent, which will be mentioned in more detail later, pro

ring or a pyrrole ring. The aromatic ketone may be a vide the metal in ion form. Thus, the metal ion may be monocyclic or a bicyclic or other polycyclic ketone. pr vided by the acetates, propionates, butyrates, ha- Aromatic ketones such as those illustrated below, and iides, halogen substituted acetates Preplehates or isomers thereof, may be employed. tyrates, or other compounds of the metal.

' The preferred metal ion for the reaction is trivalent 0 manganese, or manganic ion, Mn, which, as mentioned previously, is reducible during the reaction to CH (8) bivalent man M A ganese, or manganous ion, n 5

shown by Equations 1 and 3, the Mn is a reactant. Manganic acetate dihydrate is a Mn -producing compound. It may be formed by refluxing an acetic acid so- 0 lution of manganous acetate with potassium permanganate. Other suitable Mn -producing compounds or CH (b) mixtures include anhydrous manganic acetate, manganic propionate, and manganic butyrate; a mixture of activated (i.e., freshly prepared or acid treated) manganese dioxide and acetic acid; a mixture of manganese sesquioxide and acetic acid; and a mixture of Mn O V and acetic acid. They also include a solution of manganese chloride in acetic acid; or manganese fluoride, or

C CH (c) manganic hypophosphate dihydrate, or manganic sulfate, or manganic phosphate monohydrate, manganic pyrophosphate, each dissolved in acetic acid or one of the solvents noted below. Other higher valent manganese ions, in solution, may be of use, such as Mn, as obtained from a mixture of MnO- and acetic acid; Mn, as supplied by the manganate of sodium, potassium, ammonium, lithium, magnesium, strontium, calcium, or barium; and Mn, as supplied by the permanganate of sodium, potassium, ammonium, or magnesium. Whatever higher valent manganese ion-supplying compound is chosen, it should be soluble in the reaction mixture. In addition to the foregoing higher valent manganese ions, it is feasible to employ mixtures of ions, such as Mn plus any of Mn, Mn, Mn or Mn; or Mn plus any of Mn, Mn, or Mn; or Mn plus Mn or Mn"; or Mn" plus Mn. Such mixtures may be supplied by suitable mixtures of the foregoing source compounds. The Mn ion may be supplied by any soluble manganous compound, such as the acetate, propionate, nitrate, oxide, hydroxide, chloride, sulfate, phosphate, or perchlorate.

The manganese source compound may be added per se to the reaction mixture, or if desired it may be formed in situ. In situ formation may suitably be performed by adding to the reaction mixture a manganous compound like manganous acetate together with a solvent therefor like acetic acid and also adding an oxidizing agent so that the Mn ion is oxidized at least to Mn ion. Other manganous compounds include those named in the preceding paragraph, and other solvents include alkali metal acetates and carbonates as well as those described below. Suitable oxidizing agents include nitric acid, potassium permanganate, chlorine, oxygen, air, potassium manganate, cerium ammonium nitrate, cobaltic acetate, various peroxides like peracetic acid and hydrogen peroxide, or intermediate peroxides or hydroperoxides resulting from the air oxidation of hydrocarbons. Electrochemical oxidation is a suitable oxidizing procedure.

The reaction preferably should be carried out in the presence of a solvent. The olefin, acetylene, or aromatic ketone may in themselves act as the solvent. Primarily, the solvent is employed to maintain the metal ion compound in a state of solution. On the other hand, it is not essential that the metal ion compound be in a state of solution since the reaction mixture may be in a heterogeneous phase condition such as where the metal ion compound is in the form of a slurry. Where a solvent additional to the reactants is to be employed, it may be any liquid which is inert with respect to the reaction and has sufficient polarity to effect solution of the metal ion compound. Preferably, acetic acid is employed as the solvent. However, other carboxylic acids, such as propionic, butyric, and pentanoic acids, may be employed. Carboxylic acid esters, nitriles, nitro compounds such as nitromethane, sulfonic acids and sulfonic acid esters may also be employed.

Considering now the conduct of the reaction, the concentration of the olefin or acetylene may range from 0.01 to molar. Preferably, 0.25 to 1 mole of olefin or acetylene per mole of manganic or other higher valent metal ion may be employed. The aromatic ketone is present at least in an amount to provide 1 mole per mole of olefin or acetylene. Preferably, it should be in excess. A solvent, as previously noted, may also be present. The solvent, which may be acetic acid also as previously noted, may be present in an amount sufficient to dissolve the olefin or acetylene, the metal compound, and the aromatic ketone. The reaction is preferably performed at temperatures ranging from about 40 to 100 C. However, higher and lower temperatures may also be used. Temperatures above boiling are of use but, in this case, the reaction is performed under pressure to maintain aliquid phase. Reaction times generally extend from an hour or less to 5 or 10 hours or more. An inert atmosphere, such as one of nitrogen, carbon dioxide, helium, and the like, is desirably maintained over the reaction mixture to avoid oxidation by air.

At the conclusion of the reaction, separation of the product may be effected as by conventional distillation, extraction, fractional crystallization, and the like with or without the aid of conventional filtration or centrifu gation. For example, in a reaction mixture containing the product, acetic acid, reduced manganous salt like manganous acetate, and any unreacted unsaturated compound, the mixture may be filtered to remove any solids and then subjected to distillation, using vacuum if necessary to separate the product from other components. Alternatively, the reaction mixture may be mixed with additional quantities of acetic acid sufficient to dissolve all the manganous acetate and the resulting mixture distilled under vacuum to isolate the product; in this case the manganese salt may be found in the column bottoms.

The manganous compound that is formed as a consequence of the reduction of the manganic compound may, as already indicated, be saved and used to regenerate the manganic compound. Thus, where the manganous compound is manganous acetate, it is desirably isolated from the reaction mixture, heated at 200 to 300 C. to form MnO, acetone, and carbon dioxide, and the MnO then heated in air or oxygen to form MnO M11 0 and/or Mn O.,. On dissolving these oxides in acetic acid, there is formed manganic acetate, and this solution is of use to prepare a product in accordance, say, with Equations 1 through 3 above. The acetone, of course, is valuable enough to recover.

Alternatively, the isolated manganous acetate may be dissolved in acetic acid and the solution electrolyzed, using a carbon or other suitable anode, to form manganic acetate, the resulting electrolyzed solution being directly usable in a free radical reaction. Where the manganous acetate is already in solution in acetic acid, no preliminary isolation step is necessary as such solution may be charged to the electrolysis cell and electrolyzed.

Or the isolated manganous acetate may be dissolved in water, the solution buffered to pH 6 to 8 by means of ammonium chloride or other suitable buffer, and air or oxygen passed through the solution to produce manganese sesquioxide. This oxide is filtered and dissolved in acetic acid to form a solution of manganic acetate.

The isolated manganous acetate may also be treated with an oxidizing agent like concentrated or fuming nitric acid plus acetic anhydride to produce anhydrous manganic acetate, which is useful per se in the free radical reaction.

As a further alternative, the manganous acetate, either isolated or in acetic acid solution, may be mixed with acetic acid and with activated MnO to form manganic acetate. To obtain activated MnO one can freshly prepare this oxide, or can treat an existing sample with a dilute mineral acid following this with water washing and drying.

Manganous acetate can also be oxidized to manganic acetate by treatment with potassium permanganate.

The foregoing regeneration procedures generally apply to other manganous compounds besides the acetate; and with suitable modifications they are applica- EXAMPLE 1 In this example, phenyl methyl ketone (aeetophenone) was reacted with butene-l to form a tetralone, 4-ethy1-l-tetralone, in accordance with the equation:

The reaction was carried out by adding 50 milliliters of 0.26 molar manganic acetate dihydrate (Mn(O- COCH .2H O) in acetic acid, the acetic acid containing dissolved therein percent by weight of potassium acetate, to milliliters of phenyl methyl ketone in an EXAMPLE 2 In this example, phenyl methyl ketone was reacted with isobutylene to form a tetralone, 4-dimethyl-1- tetralone, in accordance with the equation:

i CH

c 3 cn 011 c\ 0.

To 361 grams of phenyl methyl ketone in an ampule were added 600 milliliters of acetic acid containing dissolved therein grams of potassium acetate and 50 grams of manganic acetate dihydrate. The ampule was purged with nitrogen and thereafter isobutylene was bubbled through the mixture for 10 minutes. The ampule was sealed and placed in a bath maintained at a temperature of C. The reaction, which required about 2 hours, was considered to be complete with the disappearance of the brown manganic ion color. The yield of the tetralone was about 30 percent and had a boiling point of 120 C. at 2.0 millimeters of mercury.

EXAMPLE 3 In this example, phenyl methyl ketone was reacted with l-octene to form 4-n-hexy1-1-tetralone in accordance with the equation:

I C H ll (2 \CH CH2=CH -(cn -ca \en I 011 To a l-liter pyrex bomb were added 5.52 grams (0.0200 mole) of manganic acetate dihydrate, 50 milliliters of acetic acid containing dissolved therein 10 percent by weight of potassium acetate, 72.08 grams (0.600 mole) of phenyl methyl ketone, and 1.68 grams (0.0150 mole) of l-octene. The bomb was sealed and placed in a bath maintained at C. The reaction was complete after 22 minutes as indicated by the dis appearance of the brown color of the manganic ion. The acetic acid was distilled from the reaction mixture on a rotovac. The residue from the distillation was taken up in 250 milliliters of water and extracted successively with 250, 100, and 100 milliliter portions of diethyl ether. The ether extracts were neutralized by extraction with cold aqueous solution containing 10 percent by weight of sodium carbonate. The aqueous base layer was extracted once with diethyl ether. This C CH2 CH CH ether layer was combined with the three other layers previously obtained and the combined layers dried over magnesium sulfate, filtered and evaporated to give 68.08 grams of the tetralone product. The yield of product was 46 percent.

EXAMPLE 4 In this example, acetylthiophene was reacted with propylene in accordance with the formula:

--CH3 CH2: cit-c11 The procedure carried out was the same as that in Example 3. The amounts of reactants, reaction temperature, and yield of product were as follows:

Manganic acetate dehydrate 11.04 grams (0.0400 mole) Acetylthiophene 151.42 grams (1.200 moles) Propylene 1.26 grams (0.0300 mole) potassium acetate in acetic acid 350 milliliters Reaction temperature 70 C, Yield EXAMPLE 5 In this example, acetylthiophene was reacted with cis-2-butene in accordance with the formula:

--c-c1r cn cu =CH-CH3 The procedure carried out was the same as that in Example 3. The amounts of reactants, reaction temperature, and yield of product were as follows:

Manganic acetate dihydrate l 1.04 grams (0.0400 mole) Acetylthiophene 12.62 grams (0.100 mole) .Cis-2-butene 8.41 grams (0.] mole) 10% potassium acetate in acetic acid 650 milliliters Reaction temperature Yield 43%.

EXAMPLES 6 10 requirement of 2 moles of manganic ion per mole of polycyclic ketone.

TABLE I Example Number Ke tone Olefin Polycyclic Ke tone Yield VI Phenyl methyl Butane-2 0 40% ke tone I H H3 v11 Phenyl methyl CH -CH-S1 (CH 3 29% Ice tone 0 VIII Phenyl e thyl 0c tene- 1 S 1 (CH3 )3 2 97.,

ke tone 0 l CH TABLE l-Continued Example Number Ketone Olefin Polycyclic Ketone Yield IX Phenyl @5591 Butane-Q 53% ketone H CH X Acetylthiophene Octene-l 3 347.

EXAMPLE ll Phenyl methyl ketone reacted with butadiene in the presence of manganic acetate yields 4-vinyl-alphatetralone as the product.

EXAMPLE 12 A 4-n-alkyl-l-tetralone, such as the 4-n-hexyl-ltetralone prepared in Example 3, is dehydrogenated in the presence of a platinum catalyst. The dehydrogenated product is an alpha-naphthol, i.e.,

where R is the alkyl group in the tetralone. The alphanaphthol can be treated with ammonia to produce an alpha-naphtholamine:

Both the alpha-naphthol and the alpha-naphtholamine are, as indicated, antioxidants. The alpha-naphthol may be converted to alpha-naphthol carbamate, which is an insecticide,

The product of Example 4 is dehydrogenated and the dehydrogenated product is converted to the carbamate:

The product is an insecticide.

EXAMPLE 14 In this example, the ketone:

O 0- c cn O c cu is reacted with the olefin, R CH CH where R is an alkyl group, in accordance with the invention, to give the product:

C-0 0 Cl-l H C I pu C r1 This latter product, upon hydrolysis, gives the compound:

polycyclic ketonc having at least two rings, at least one of which is an aromatic ring and the other of which contains, as part of its ring structure, the carbom atom of a keto group, these two rings sharing two carbon atoms as part of their ring structure, said method comprising reacting an olefin selected from the group consisting of ethylene, propylene, n-butylene, isobutylene, pentene, hexene, heptene, octene, allene, butadiene, hexadiene, heptadiene, diisobutenyl, and hexatriene, or an acetylene selected from the group consisting of ethine, allylene, butyne, pentyne, hexyne, heptyne, octyne, butenyne, 1,6-heptadiene-3-yne, and 1,7- octaenyne with an aromatic ketone selected from the group consisting of phenyl methyl ketone, phenyl ethyl ketone, naphthyl methyl ketone, acetylanthracene, acetylpyridine, acetylfuran, and acetylthiophene in the presence of a metal ion of manganese, cerium, or vanadium in a higher valent form, said metal ion being provided by a compound of said metal selected from the group consisting of the acetates, propionates, butyrates, halides, and halogen-substituted acetates, -propionates, and -butyrates of said metal, said reaction being carried out with a concentration of said olefin or acetylene in the range from 0.10 to 5 molar, the amount of said olefin being from 0.25 to 1 mole per mole of metal ion, the amount of said aromatic ketone being at least 1 mole per mole of said olefin or acetylene, the temperature being between and 100 C., and the pressure being such to maintain the reactants in the liquid phase.

2. The method of claim 1 wherein said olefin is ethylene.

3. The method of claim 1 wherein said aromatic ketone is phenyl methyl ketone.

4. The method of claim 1 wherein said metal ion is manganic ion provided by manganic acetate.

5. The method of claim 1 wherein said reaction is carried out in the presence of a solvent for said compound of said metal additional to said olefin, said acetylene, and said aromatic ketone.

6. The method of claim 5 wherein said solvent is acetic acid.

7. The method of claim 6 wherein said olefin is ethylene, said aromatic ketone is phenyl methyl ketone, and said metal ion is manganic ion provided by manganic acetate.

8. The method of claim 6 wherein said olefin is butene-l, said aromatic ketone is phenyl methyl ketone, and said metal ion is manganic ion provided by manganic acetate.

9. The method of claim 6 wherein said olefin is isobutylene, said aromatic ketone is phenyl methyl ketone, and said metal ion is manganic ion provided by manganic acetate.

10. The method of claim 6 wherein said olefin is loctene, said aromatic ketone is phenyl methyl ketone, and said metal ion is manganic ion provided by manganic acetate.

11. The method of claim 6 wherein said olefin is propylene, said aromatic ketone is acetylthiophene, and said metal ion is manganic ion provided by manganic acetate.

12. A method of preparing a polycyclic ketone, said polycyclic ketone having at least two rings, at least one of which is an aromatic ring and the other of which contains, as part of its ring structure, the carbon atom of a keto group, these two rings sharing two carbon atoms as part of their ring structure, said method comprising reacting ethylene with phenyl methyl ketone in the presence of manganic ion provided by manganic acetate and in the presence of acetic acid as a solvent for said manganic acetate, said reaction being carried out with a concentration of said ethylene in the range from 0.10 to 5 molar, the amount of said ethylene being from 0.25 to 1 mole per mole of said manganic ion, the concentration of said phenyl methyl ketone being at least 1 mole per mole of said ethylene, the temperature being between 40 and C., and the pressure being such to maintain the reactants in the liquid phase.

mg? UNITED sums PlTENT omen CERTIFICATE OF CORRECTION Paton: No- 111350.612 t-1mm Inventofls) EL AHMADI I. 1mm and RALPH M. DESSAU It is certified that error appo'ia'to 1n the lbOVI-idtfltified pauug. and that aid Lotta-o Paton: are hereby oozroctod as shown below:

Column 5, line 3 8- "Aceylenea" should be --a.cetylenea--.

Signed and sealed this 1st day of April 1975.

(SELL) Attest:

C. I- ARSHALL DANN Commissioner of Patents and Trademarks RUTH C. i-iASON Attesting Officer 

1. A METHOD OF PREPARING A POLYCYCLIC KETONE, SAID POLYCYCLIC KETONE HAVING AT LEAST TWO RINGS, AT LEAST ONE OF WHICH IS AN AROMATIC RING AND THE OTHER OF WHICH CONTAINS, AS PART OF ITS RING STRUCTURE, THE CARBON ATOM OF A KETO GROUP, THESE TWO RINGS SHARING TWO CARBON ATOMS AS PART OF THEIR RING STRUCTURE, SAID METHOD COMPRISING REACTING AN OLEFIN SELECTED FROM THE GROUP CONSISTING OF ETHYLENE, PROPYENE, N-BUTYLENE, ISOBUTYLENE, PENTENE, HEXENE, HEPTENE, OCTENE, ALLENE, BUTADIENE, HEXADIENE, HEPTADIENE, DIISOBUTENYL, AND HEXATRIENE, OR AN ACETYLENE SELECTED FROM THE GROUP CONSISTING OF ETHINE, ALLYLENE, BUTYNE, PENTYNE, HEXYNE, HEPTYNE, OCTYNE, BUTENYNE, 1,6-HEPTADIENE-3-YNE, AND 1,7-OCTAENYNE WITH AN AROMATIC KETONE SELECTED FROM THE GROUP CONSISTING OF PHENYL METHYL KETONE, PHENYL ETHYL KETONE, NAPHTHYL METHYL KETONE, ACETYLANTHRACENE, ACETYLPYRIDINE, ACETYLFURAN, AND ACETYLTHIOPHENE IN THE PRESENCE OF A METAL ION OF MANGANESE, CERIUM, OR VANADIUM IN A HIGHER VALENT FORM, SAID METAL ION BEING PROVIDED BY A COMPOUND OF SAID METAL SELECTED FROM THE GROUP CONSISTING OF THE ACETATES, PROPIONATES, BUTYRATES, HALIDES, AND HALOGENSUBSTITUTED ACETATES, -PROPIONATES, AND -BUTYRATES OF SAID METAL, SAID REACTION BEING CARRIED OUT WITH A CONCENTRATION OF SAID OLEFIN OR ACETYLENE IN THE RANGE FROM 0.10 TO 5 MOLAR, THE AMOUNT OF SAID OLEFIN BEING FROM 0.25 TO 1 MOLE PER MOLE OF METAL ION, THE AMOUNT OF SAID AROMATIC KETONE BEING AT LEAST 1 MOLE PER MOLE OF SAID OLEFIN OR ACETYLENE, THE TEMPERATURE BEING BETWEEN 40* AND 100*C., AND THE PRESSURE BEING SUCH TO MAINTAIN THE REACTANTS IN THE LIQUID PHASE.
 2. The method of claim 1 wherein said olefin is ethylene.
 3. The method of claim 1 wherein said aromatic ketone is phenyl methyl ketone.
 4. The method of claim 1 wherein said Metal ion is manganic ion provided by manganic acetate.
 5. The method of claim 1 wherein said reaction is carried out in the presence of a solvent for said compound of said metal additional to said olefin, said acetylene, and said aromatic ketone.
 6. The method of claim 5 wherein said solvent is acetic acid.
 7. The method of claim 6 wherein said olefin is ethylene, said aromatic ketone is phenyl methyl ketone, and said metal ion is manganic ion provided by manganic acetate.
 8. The method of claim 6 wherein said olefin is butene-1, said aromatic ketone is phenyl methyl ketone, and said metal ion is manganic ion provided by manganic acetate.
 9. The method of claim 6 wherein said olefin is isobutylene, said aromatic ketone is phenyl methyl ketone, and said metal ion is manganic ion provided by manganic acetate.
 10. The method of claim 6 wherein said olefin is 1-octene, said aromatic ketone is phenyl methyl ketone, and said metal ion is manganic ion provided by manganic acetate.
 11. The method of claim 6 wherein said olefin is propylene, said aromatic ketone is acetylthiophene, and said metal ion is manganic ion provided by manganic acetate.
 12. A method of preparing a polycyclic ketone, said polycyclic ketone having at least two rings, at least one of which is an aromatic ring and the other of which contains, as part of its ring structure, the carbon atom of a keto group, these two rings sharing two carbon atoms as part of their ring structure, said method comprising reacting ethylene with phenyl methyl ketone in the presence of manganic ion provided by manganic acetate and in the presence of acetic acid as a solvent for said manganic acetate, said reaction being carried out with a concentration of said ethylene in the range from 0.10 to 5 molar, the amount of said ethylene being from 0.25 to 1 mole per mole of said manganic ion, the concentration of said phenyl methyl ketone being at least 1 mole per mole of said ethylene, the temperature being between 40* and 100* C., and the pressure being such to maintain the reactants in the liquid phase. 